Sulfur dyestuffs of the phthalocyanine series



United States SULFUR DYESTUFFS 9F THE PHTHALOCYANINE SERIES No Drawing.Application December 19, 1956 Serial No. 629,239

Claims priority, application Germany July 2, 1953 8 Claims. (Cl.26fi-314.5)

This invention relates to new sulfur dyestuffs of the phthalocyanineseries and a process for producing the same and is acontinuation-in-part of application Serial No. 440,533, filed June 30,1954, and a continuation-inpart of application Serial No. 528,824, filedAugust 16, 1955.

It is known in the prior art that sulfur dyestuffs of the phthalocyanineseries ranging from green to blue shades can be produced by reducingphthalocyanine sulfochlorides.

The dyestuffs of the present invention are generally mixtures of metalphthalocyanines containing several nitrogen-containing andsulfur-containing groups. The main components of these mixtures aredyestuffs of the formula:

neg;

wherein Me is selected from the group consisting of nickel, copper, andcobalt. These sulfur dyestuffs are of a greenish-grey to bluish-greyshade, shades unknown in the phthalocyanine series prior to thisinvention. As in the case of other sulfur dyestuffs, the dyestuffs ofthe present invention are oxidized during dyeing to contain disulfidegroups instead of the SH groups of the above formula.

In accordance with the process of the present invention, the newdyestuffs are formed by reacting a metal tetramino phthalocyanine (themetal being of the group consisting of nickel, copper, and cobalt),produced in situ or as an initial reactant, with chlorosulfonic acid ata temperature of between about 70 C. and 150 C. and then reducing theresulting product, preferably with iron or zinc, in a mineral acidmedium.

More particularly, and in the event an aforesaid metal tetraminophthalocyanine is employed as an initial reactant, i. e., instead offorming the same in situ, it is treated with chlorosulfonic acid at atemperature within the aforesaid range, and subsequently reduced toproduce the new and novel dyestuffs (see Examples 2-4.)

Introduction of mercapto-groups into the metal tetramine phthalocyaninesmay, however, also be effected by atent O 2,832,789 Patented Apr. 29,1958 "ice the action of sulfur chloride in the presence ofch1orosulfonic acid as a solvent (see Example 5). Furthermore the twomethods, i. e. the reaction wtih chlorosulfonic acid with subsequentreduction and the reaction with sulfur chloride, may be combined (seeExample 6.)

The metal tetramino phthalocyanines are usually prepared by a reductionof the corresponding metal tetranitro phthalocyanines. The reduction maybe combined with the introduction of the mercapto groups by treating themetal tetranitro phthalocyanines with sulfur and chlorosulfonic acid(see Example 1.)

However, and in the event it is desired to produce the metaltetraminophthalocyanine in situ, this may be done by simultaneoustreatment of a metal phthalocyanine with hydroxylamine andchlorosulfonic acid under the same conditions of temperature andsubsequently reducing the resulting reaction product by the use of ametal, such as iron or zinc in a mineral acid medium. In the case of thereaction with hydroxylamine and cholorsulfon ic acid, it is preferred toemploy a catalyst which is a compound of an element belonging to groupVa or Via of the periodic system. Preferred catalysts are ammoniummolybdate or vanadium pentoxide. As illustrated in the Examples 7 to 12hereinafter, variation in the con centration. of hydroxylamine in thereaction mixture permits variation of the shades of the new dyestuffsfrom a sodium sulfide bath on cotton. This is a particularlyadvantageous feature of this embodiment of the process for producingdyestuiis in accordance with the present invention.

When producing dyestuffs by directly reacting with chlorosulfonic acid,a metal tetramino phthalocyanine which is prepared from 4-nitrophthalicacid and in which, therefore, the position of the amino groups is clear,particularly valuable compounds are obtained, the main component ofwhich is represented by the formula:

wherein one of each of R R R and R is NH and the other of each of R R Rand R is hydrogen and Me is selected from the group consisting ofnickel, cop per, and cobalt and the SH-groups replace one of the 3H-atoms of each benzene nucleus.

As illustrated in the examples appearing hereinafter, wherein all partsare parts by weight and all temperatures are of the centigrade scale,the dyestuffs of the present invention possess good fastness properties,fastness to light being exceptional as compared wtih many otherdyestuffs.

Example I 15.1 parts of tetra-(4-nitro)-copper phthalocyanine areintroduced into 227 parts of chlorosulfonicacid. After adding 12.8:parts of sulfur, the mixture, is cautiously heated until an exothermicreaction begins, i. e. to 65- 70. The temperature is then raised to 135and the mass is stirred for hours at 135. The reaction mass is pouredinto water or upon ice and worked up in 'a known manner. The blackpowder thus obtained dyes cotton, from a bluish dark-green sodiumsulfide solution, greenish olive-grey shades of a good fastness towashing and a very good fastness to light. If the reaction is performedat 90, a product is obtained which delivers somewhat more bluish dyeingswith the same fastness properties.

Upon replacing the tetra-(4-nitro)-copper phthalocyanine used in theabove example by 15 parts of tetra-(4- n'itro)-cobalt phthalocyanine adyestutf with closely analogous properties is obtained.

Example II 12.7 parts of tetramino copper phthalocyanine (prepared in aknown manner from a nitrating mixture of phthalic acid, containing 3-and 4-nitrophthalic acid) are stirred in a mixture of 190.5 parts ofcholorosulfonic acid for 2 hours at 125. The reaction mass is pouredonto a mixture of 857 parts of ice, 200 parts of concentratedhydrochloric acid and 40 parts of iron powder and the temperature israised within 24 hours, with stirring, to 8590. The dyestufi is thenisolated in the usual manner. This black amorphous product dissolves inconcentrated sulfuric acid with a dull dark-green color and dyes cotton,from a dull and bluish green sodium sulfide solution, greenish-greyshades of 'a good resistance to washing and an outstanding fastness tolight.

Example III 12.6 parts of tetramino nickel phthalocyanine (prepared in aknown manner from a nitrating mixture of phthalic acid, containing 3-and 4-nitrophthalic acid) are stirred in a mixture of 190.5 parts ofchlorosulfonic acid for 2 hours at 125 the subsequent treatment being asindicated in Example II. The product thus obtained dissolves inconcentrated sulfuric acid with a bluish darkgreen color and dyescotton, from a dull and bluish green sodium sulfide solution,greenish-grey shades of a good resistance to washing and a very goodfastness to light.

A similar product is obtained by starting from tetramino cobaltphthalocyanine and employing the same conditions.

Example IV 25.4 parts of tetra-4-amino copper phthalocyanine (preparedfrom 4-nitrophthalimide in a known manner) are stirred in 381 parts ofchlorosulfonic acid for 2 hours at 135 The reaction mass is poured ontoa mixture of 935 parts of ice, 762 parts of water, 800 parts ofconcentrated hydrochloric acid and 80 parts of iron powder, thetemperature is raised within 24 hours to 85-90 and the dyestufi" isisolated in the usual manner. The black amorphous product dissolves inconcentrated sulfuric acid with a dull dark-green color. It dyes cotton,from a bluish dark-green sodium sulfide solution, greenish olivegreyshades of a good resistance to washing and an outstanding fastness tolight.

Example V 12.7 parts of tetra-(4-amino)-copper phthalocyanine areintroduced into a mixture of 191 parts of chlorosulfonic acid and 54parts of sulfur chloride (S CI Upon heating to about 90100, the reactionstarts with the liberation of hydrogen chloride. During about 50 60minutes the mass is heated to 135 and is then stirred for 2 hours atthis temperature. The reaction mixture is then poured into Water or uponice and the product is isolated in a known manner. A black powder isobtained which dyes cotton, from a sodium sulfide solution, greenisholive-grey shades of a good fastness to washing and a very good fastnessto light.

Upon replacing the tetra-(4-amino)-copper-phthalocyanine used in thisexample by an equal amount of tetra- (3+4)-amino-copper phthalocyanine(prepared in a known manner from a mixture of 3- and 4-nitrophthalicacid obtained by nitrating phthalic acid anhydride), a product is formedwhich dyes cotton, from a bluish blackgrey sodium sulfide solution,considerably more bluish olive grey shades with the same overallproperties as those of the aforesaid product.

If instead of the tetra-(4-amino)-copper phthalocyanine employed in thisexample, 12.6 parts of tetra- (4-arninol-cobalt phthalocyanineare usedand the mass is stirred for 2 hours at 90 instead of at 135, a productis obtained which as to its shade is very close to the copper dyestuff.

Example VI 12.7 parts of tetra-4-amino-copper phthalocyanine are stirredin 191 parts of chlorosulfonic acid for 1 hour at 135. Subsequently, atan equal temperature and within l0-20 minutes, 27 parts of sulfurchloride are added by dropping in with stirring for another hour at 135.For the purpose of a reduction, the reaction mixture is poured onto amixture of 381 parts of ice, 400 parts of crude concentratedhydrochloric acid and 26 .8 parts of iron powder. After stirring forseveral hours at about 50, the dyestuff is isolated in a usual manner.It dyes cotton, from a dirty black-grey sodium sulfide solution,

greenish olive-grey shades of a good fastness to washing and a very goodfastness to light. In comparison to the products mentioned in thepreceding examples, it is distinguished by an especially great strengthof color.

Upon replacing the tetra-(4-am'ino)-copper phthalocyanine used in thisexample by an equal amount of tetra- (3+4)-amino-copper phthalocyanine(prepared in a known manner from a mixture of 3- and 4-nitrophthalicacid obtained by nitrating phthalic acid anhydride), a dyestufi" isobtained which dyes cotton, from a bluish black-grey sodium sulfidesolution, a considerably bluer shade. The product possesses analogousfastness properties as the other dyestuff of this example.

Example VII 23 parts of copper phthalocyanine, 15.6 parts ofhydroxylarnine sulfate and 0.11 part of ammonium molybdate are stirredin 345 parts of chlorosulfonic acid for 2 hours at At the sametemperature, there are added by drops within 10-20 minutes 54 parts ofsulfur chloride and the mass is stirred again for 1-2 hours at 125. Thereaction mixture is poured onto a mixture of 690 parts of ice, 500 partsof crude concentrated hydrochloric acid and 54 parts of iron powder.After stirring the mass for several hours at about 50, the dyestutf isobtained. The product dyes cotton, from a violet-tinged black-greysodium sulfide solution, greenish olive-grey shades. The dyeings possessa good fastness to washing and a very good fastness to light.

If the amount of the sulfur chloride is diminished to 4-0.5 or 27 parts,dyestufis of almost equal properties are obtained. If the amount of thehydroxylamine sulfate is increased from 15.6 to 17.5 parts, a product isformed which is distinguished from that mentioned above only in a verysmall degree.

Example VIII 23 parts of copper phthalocyanine and 0.23 part of ammoniummolybdate are introduced into 460 parts of chlorosulfonic acid. Afteradding 26 parts of hydroxylamine sulfate, the mixture is heatedgradually to and stirred for 2 hours at this temperature. The reactionmass is then poured onto a rapidly stirred mixture of 1380 parts of iceand 80 parts of iron powder. After stirring for 24 hours at 50, theblack-green dyestufi is filtered by suction and freed of iron salts andacids by washing it. The product dyes cotton, from'a sodium sulfidebath, greenish grey shades of good fastnessproperties.

The same product is obtained when ammonium molybdate is replaced byvanadium pentoxide or when iron powder is replaced by zinc powder.

Example IX 23 parts of copper phthalocyanine and 0.2 part of ammoniummolybdate are introduced into 342 parts of chlorosulfonic acid. Afteradding 26 parts of hydroxylamine sulfate, the temperature of the mixtureis raised to 135, a subsequent stirring being performed for 2 hours atthis temperature. The reaction mass is poured onto a mixture of 1030parts of ice and 80 parts of iron powder and the mass is heated withoutdelay to 9095. After stirring during 3 hours at the said temperature,the dyestufi thus formed is worked up as set forth in Example VHI. Theshade of this product is somewhat more green ish than that of thedyestufl obtained according to Example VIII.

If the hydroxylamine sulfate used in this Example is replaced by 22parts of hydroxylamine hydrochloride, the same dyestulf is obtained.

Example X which is absorbed from a sodium sulfide solution by cotton,yielding a bluish grey shade.

If the amount of chlorosulfonic acid used in the above example islessened to 225 parts, the same dyestutf is obtained.

Example XI 22.8 parts of cobalt phthalocyanine and 0.2 part of ammoniummolybdate are introduced into 342 parts of chlorosulfonic acid. Afteradding 22 parts of hydroxylamine hydrochloride, the mixture is stirredfor 2 hours at 125. The reaction mass is poured onto a mixture of 1030parts of ice and 80 parts of iron powder. The mass is then stirred for30 minutes at 20, 2 hours at 50-55, and 1 hour at 95 After working up asdescribed in the previous examples, the product obtained dyes cottonfrom a sodium sulfide solution to bluish grey shades.

If using instead of the 22 parts of hydroxylamine hydichloride indicatedin the abov example only 16.6 parts thereof, a very similar product isobtained.

Example XII 22.8 parts of nickel phthalocyanine and 0.2 part of ammoniummolybdate are introduced into 342 parts of chlorosulfonic acid. Afteradding 19.7 parts of hydroxylamine sulfate, the mixture is stirred for 2hours at 125. The mass is poured onto a mixture of 1380 parts of ice, 80parts of iron powder and 300 parts of concentrated hydrochloric acid andis stirred, while raising the temperature of 80-90, until the reactionis complete. The product worked up in the same way as in the precedingexamples has very similar properties to substances described in theExamples VIII and IX.

The foregoing description of the present invention is for the purpose ofillustration only and is not limiting to the scope thereof which is setforth in the claims.

We claim:

1. A process for forming a dyestufi which comprises reacting a metaltetramino phthalocyanine, wherein the metal is a member of the groupconsisting of nickel, copper and cobalt, with chlorosulfonic acid at atemperature of between about 70 C. and 150 C. and, thereafter, reducingthe reaction product with a metal of the group consisting of iron andzinc in a mineral acid medium.

6 2. A process for forming a dyestuff which comprises reacting coppertetra-(4)-amino-phthalocyanine with chlorosulfonic acid at a temperatureof between C.

and C. and, thereafter, reducing the reaction prod-- uct with iron in amineral acid medium.

3. The process of claim 1, wherein the metal tetramino phthalocyanine isproduced in situ by reacting the corresponding metal phthalocyanine withhydroxylamine in the presence of a compound of the group consisting ofammonium molybdate and vanadium pentoxide.

4. The process of claim 3 wherein the corresponding metal phthalocyanineis nickel phthalocyanine.

5. The compound of the formula:

wherein Me is selected from the group consisting of nickel, copper andcobalt.

6. The compound of claim 5 wherein Me is nickel. 7. The compound of theformula:

wherein one of each of R R R and R is NH; and the other of each of R R Rand R is hydrogen and and Me is selected from the group consisting ofnickel, copper, and cobalt and the SH-groups replace one of the 3H-atoms of each benzene nucleus.

8. The compound of claim 7 wherein Me is copper.

References Cited in the tile of this patent UNITED STATES PATENTS2,219,330 Nadler et al. Oct. 29, 1940 2,266,404 Bienert et al. Dec. 16,1941 2,280,072 Haddock Apr. 21, 1942 2,484,300 Mayhew Oct. 11, 19492,613,128 Baumann Oct. 7, 1952

1. A PROCESS FOR FORMING A DYESTUFF WHICH COMPRISES REACTING A METALTETRAMINO PHTHALOCYANINE, WHEREIN THE METAL IS A MEMBER OF THE GROUPCONSISTING OF NICKEL, COP PER AND COBALT, WITH CHLOROSULFONIC ACID AT ATEMPERATURE OF BETWEEN ABOUT 70*C. AND 150*C. AND, THEREAFTER, REDUCINGTHE REACTION PRODUCT WITH A METAL OF THE GROUP CONSISTING OF IRON ANDZINC IN A MINERAL ACID MEDIUM.